Meta-bifunctional benzenes

ABSTRACT

WHEREIN A is selected from the groups   Meta-bifunctional of the general formula These compounds possess herbicidal activity.

United States Patent [191 Olin et a1.

14 Feb. 11, 1975 META-BIFUNCTIONAL BENZENES [75] Inventors: John F. Olin, Ballwin; Philip C.

Hamm, Glendale. both of Mo.

[73] Assignee: Monsanto Company, St. Louis, Mo. [22] Filed: May 26, 1970 [21] Appl. No.: 40,742

Related U.S. Application Data [63] Continuation of Ser. No. 647,202, June 19, 1967,

abandoned.

[52] U.S. Cl 260/472, 71/94, 71/95, 71/99, 71/100, 71/106, 71/111, 71/118,

260/552 R, 260/553 A, 260/558 R, 260/559 R, 260/562 A, 260/562 R, 260/562 P,

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Paul .1. Killos Attorney, Agent, or FirmWilliam T. Black [57] ABSTRACT Meta-.bifunctional of the general formula wherein A is selected from the groups 11 -N c R19 '1 -N-C-Z -R (4) R22 z R23 I H -N N These compounds possess herbicidal activity.

12 Claims, N0 Drawings 1 META-BIFUNCTHONAL BENZENES This application is a continuation-in-part of application Ser. No. 647,202, filed June 19, 1967, now abandoned.

This invention relates to novel meta-bifunctional substituted benzenes. This invention further relates to herbicidal compositions and methods of herbicidal use utilizing the novel meta-bifunctional substituted benzenes of this invention.

The novel meta-bifunctional substituted benzenes of this invention are of the formula R l 2 l I n c R wherein Z is selected from the group consisting of oxygen and sulfur;

R is selected from the group consisting of I. hydrogen,

II. R [B], wherein B is selected from the group consisting of carbonyl and oxygen; R is selected from the group consisting of alkyl having a maximum of 12 carbon atoms, alkenyl having a maximum of 7 carbon atoms and alkynyl having at least 3 and a maximum of 6 carbon atoms; and n is an integer from to l; and

Ill. R 0 [R 0], R -wherein R is alkylene of not more than 4 carbon atoms; R is alkylene of not more than four carbon atoms; R is selected from the group consisting of alkyl and alkenyl of not more than 6 carbon atoms and m is an integer from O to l;

R is selected from the group consisting of 1. hydrogen,

ll. hydrocarbyl selected from the group consisting of alkyl having a maximum of 12 carbon atoms, alkenyl having a maximum of 8 carbon atoms, alkynyl having a maximum of 6 carbon atoms and haloalkyl having a maximum of 6 carbon atoms and a maximum of 3 halogen atoms;

lll. R 0 [R O],, R wherein R R R and m are as previously defined,

IV. cycloalkyl and alkylcycloalkyl having 3 to 7 ring carbon atoms and a maximum of4 chain carbon atoms;

V. phenyl and substituted phenyl having a maximum of 2 substituents said substituent being selected from the group consisting of halogen, alkyl having a maximum of 4 carbon atoms and COOH; and

VI. aralkyl of the formula R c R l H2) 9 1 wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of4 carbon atoms, alkenyl having a maximum of 3 carbon atoms and haloalkyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms and haloalkyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms; R is independently selected from the group consisting of alkyl having a maximum of 4 carbon atoms, alkoxy having a maximum of2 carbon atoms, COOH, and halogen; p is one of the integers zero to two; and q is one of the integers zero to two; and

A is selected from the group consisting of wherein Z and Z are each independently selected from the group consisting of oxygen and sulfur;

R is selected from the group consisting of alkyl having a maximum of 15 carbon atoms, alkenyl having a maximum of 12 carbon atoms, chloroallcyl having a maximum of 15 carbon atoms and a maximum of 3 halogen atoms, chloroalkenyl having a maximum of 12 carbon atoms and a maximum of 3 halogen atoms, alkoxyalkyl having a maximum of 12 carbon atoms, cycloalkyl having 3 to 7 ring carbon atoms and a maximum of 4 chain carbon atoms, phenyl, substituted phenyl having a maximum of 2 substituents, said substituents being selected from the group consisting of halogen, nitro and alkyl having maximum of4 carbon atoms, CH CH O phenyl, CH CIH O naphthyl, CH CH CH phenyl, the group wherein R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms chloroalkyl having a maximum of 3 carbon atoms and a maximum of 3 halogen atoms, chloroalkenyl having a maximum of 3 carbon atoms and 3 halogen atoms, provided that only one of R and R can be alkenyl or chloroalkenyl; R is selected from the group consisting of halogen, alkyl having a maximum of 4 carbon atoms, nitro, alkoxy having a maximum of 3 carbon atoms, and r is one of the integers zero to two; the group wherein R is selected from the group consisting of alkyl and alkenyl each having a maximum of 4 carbon atoms, provided that R' is other than alkenyl where either R or R is alkenyl, and R", R and r are as previously defined; and the group wherein R is selected from the group consisting of phenyl and naphthyl; R is selected from the group consisting of hydrogen, alkyl having a maximum of 6 carbon atoms; cycloalkyl having to 7 carbon atoms, alkenyl having a maximum of 3 carbon atoms and a maximum of 3 halogen atoms, chloroalkenyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms; R and R can together with the nitrogen atom form a group selected from the group consisting of wherein R is alkyl having a maximum of 3 carbon atoms and S is one of the integers zero to two;

wherein Z is selected from the group consisting of oxygen and sulfur;

R is selected from the group consisting of 1. hydrogen,

ll. R [B], wherein B is selected from the group consisting of carbonyl and oxygen, R is selected from the group consisting of alkyl having a maximum of 12 carbon atoms, alkenyl having a maximum of 7 carbon atoms and alkynyl having at least 3 and a maximum of 6 carbon atoms; and n is an integer from O to l; and

Ill. R 0 [R O],,, R wherein R is alkylene of not more than 8 carbon atoms; R is alkylene of not more than 4 carbon atoms; R is selected for the group consisting of alkyl and alkenyl of not more than 6 carbon atoms; and m is an integer from O to l; and

R is selected from the group consisting of 1. hydrogen,

ll. hydrocarbyl selected from the group consisting of alkyl having a maximum of carbon atoms, alkenyl having a maximum of 8 carbon atoms, alkynyl having at least 3 and a maximum of6 carbon atoms and haloalkyl having a maximum of 6 carbon atoms and a maximum of 3 halogen atoms;

lll. R 0 [R O],,, R -wherein R R R and m are as previously defined,

lV. cycloalkyl and alkylcycloalkyl having 3 to 7 ring carbon atoms and a maximum of4 chain carbon atoms;

V. phenyl and substituted phenyl having a maximum of 2 substituents said substituent being selected from the group consisting of halogen, alkyl having a maximum of 4 carbon atoms and COOl-l; and

5 VI. aralkyl of the formula wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms and haloalkyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms, R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms and haloalkyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms; R is independently selected from the group consisting of alkyl having a maximum of4 carbon atoms, alkoxy having a maximum of 2 carbon atoms,, COOl-l, and halogen; p is one of the integers zero to two; and q is one of the integers zero to two;

wherein Z and Z are each independently selected from the group consisting of oxygen and sulfur;

R is selected from the group consisting of hydrogen,

alkyl having a maximum of 6 carbon atoms and alkenyl having a maximum of 6 carbon atoms; and

R is selected from the group consisting of alkyl having a maximum of 8 carbon atoms, alkenyl having a maximum of 6 carbon atoms, cycyloalkyl having from 3 to 7 ring carbon atoms; cyclohexenyl, phenyl, substituted phenyl having a maximum of 2 substituents said substituents being selected from the group consisting of halogen, nitro and alkyl having a maximum of 4 carbon atoms, the group and the group R R15 R 2 (I; cu

wherein R", R, R, R and r are as previously defined; and

N c N\ wherein Z' is selected from the group consisting of oxygen and sulfur, R is selected from the group consisting of hydrogen, alkyl having a maximum of 8 carbon atoms and alkenyl having a maximum of 6 carbon atoms; R is selected from the group consisting of alkyl having a maximum of 12 carbon atoms, alkenyl having a maximum of 7 carbon atoms, alkoxy having a maximum of 6 carbon atoms, chloroalkyl having a maximum of 6 carbon atoms and a maximum of 3 halogen atoms, chloroalkenyl having a maximum of 6 carbon atoms and a maximum of 3 halogen atoms, phenyl, substituted phenyl having a maximum of 2 substituents said substituents being selected from the group consisting of halogen, nitro and alkyl having a maximum of 4 carbon atoms, the group R a; l C

and'the group 14 12 F15 R r l c ca wherein R R R, R and r are as previously defined; R is selected from the group consisting of hydrogen, alkyl havig a maximum of 12 carbon atoms and alkenyl having a maximum of 8 carbon atoms; R and R can with the nitrogen form the group selected from the group consisting of and wherein R and s are as previously defined.

As a first preferred embodiment of this invention are the compounds in which R is selected from the group consisting of hydrogen, alkoxy having a maximum of 6 carbon atoms, alkyl having a maximum of 6 carbon atoms and alkenyl having a maximum of 6 carbon atoms; 2 R and A are as previously defined.

Another preferred embodiment of this invention are the compounds of the formula wherein R is selected from the group consisting of the hydrogen and alkyl having a maximum of 6 carbon atoms; lR is selected from the group consisting of hydrogen, alkyl having a maximum of 12 carbon atoms, alkenyl having a maximum of 8 carbon atoms, haloalkyl having a maximum of 6 carbon atoms and a maximum of 3 halogen atoms; cycloalkyl having 3 to 7 ring carbon atoms, substituted cycloalkyl having 3 to 7 ring carbon atoms and a maximum of4 chain carbon atoms, phenyl, substituted phenyl having a maximum of 2 substituents said substituent being selected from the group consisting of halogen and alkyl having a maximum of 4 carbon atoms, and aralkyl of the formula wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms and haloalkyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms; R is selected from the group consisting of hydrogen, and alkyl having a maximum of 4 carbon atoms; R is independently selected from the group consisting of alkyl having a maximum of 4 carbon atoms, alkoxy having a maximum of 2 carbon atoms and halogen; p is one of the integers zero to one; and q is one of the integers zero to two; R is selected from the group consisting of alkyl having 8 to 15 carbon atoms, alkenyl having 8 to 12 carbon atoms, chloroalkyl having 4 to 12 carbon atoms and a maximum of 3 halogen atoms, chloroalkenyl having a maximum of 12 carbon atoms and a maximum of 3 halogen atoms, alkoxyalkyl having a maximum of a total of 12 carbon atoms, cycloalkyl having 3 to 7 ring carbon atoms, substituted having 3 to 7 ring carbon atoms and a maximum of 4 chain carbon atoms, Cl-l CH O phenyl, CH CH O naphthyl, CH CH=CH-phenyi, the group l 4 13 li wherein R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms, chloroalkyl having a maxi- 12 15 ig-4 C c wherein R is selected from the group consisting of alkyl and alkenyl each having a maximum of 4 carbon atoms, provided that R is other than alkenyl when either R or R is alkenyl or chloroalkenyl, and R", R, R and r are as previously defined, and the group i Q R s wherein R is alkyl having a maximum of 3 carbon atoms and s is one of the integers zero to two.

A still more preferred embodiment are the compounds of the formula R l n N-C-R R 0-C-N wherein R is selected from the group consisting of hydrogen and alkyl having a maximum of 3 carbon atoms;

R is selected from the group consisting of alkyl having at least 8 and a maximum of 15 carbon atoms, alkenyl having at least 7 and a maximum of 10 carbon atoms, haloalkyl having at least 3 and a maximum of 6 carbon atoms and a maximum of 3 halogen atoms, phenyl, substituted phenyl having a maximum of two substituents said substituent being selected from the group consisting of halogen and alkyl having a maximum of4 carbon atoms and aralkyl of the formula wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms and haloalkyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms; R is selected from the group consisting of hydrogen and alkyl having a maximum of 4 carbon atoms; R is independently selected from the group consisting of alkyl having a maximum of 4 carbon atoms, alkoxy having a maximum of 2 carbon atoms and halogen; p is one of the integers zero to one; and q is one of the integers zero to two; R is selected from the group consisting of alkyl having 8 to 15 carbon atoms, alkenyl having 3 to 12 carbon atoms, chloroalkyl having 4 to 12 carbon atoms and a maximum of 3 halogen atoms, chloroalkenyl having a maximum of 12 carbon atoms and a maximum of 3 halogen atoms, alkoxyalkyl having a maximum of a total of 12 carbon atoms, cycloalkyl having 3 to 7 ring carbon atoms, substituted having 3 to 7 ring carbon atoms and a maximum of4 chain carbon atoms, Cl-l Cl-l Ophenyl, CH CH Onaphthyl, CH CH=CHphenyl,

the group l2 14 R R a maximum of 3 carbon atoms; and r is one of the integers zero to two, the group 612 Fla wherein R is selected from the group consisting of alkyl and alkenyl each having a maximum of 4 carbon atoms, provided that R is other than alkenyl when either R or R is alkenyl or chloroalkenyl, and R, R, R and r are as previously defined, and the group G -Cliwherein R is alkyl having a maximum of 3 carbon atoms and s is one of the integers zero to two.

A further embodiment are the compounds of the formula wherein R is selected from the group consisting of hydrogen and alkyl having a maximum of 3 carbon atoms; R is selected from the group consisting of alkyl having at least 8 and a maximum of 15 carbon atoms, alkenyl having at least 8 and a maximum of carbon atoms, haloalkyl having at least 3 carbon atoms and a maximum of 6 carbon atoms and a maximum of 6 carbon atoms and a maximum of 3 halogen atoms, cycloalkyl having at least 3 and a maximum of 6 carbon atoms, phenyl, substituted phenyl having a maximum of 2 substituents said substituent being independently selected from the group consisting of halogen and alkyl having a maximum of 4 carbon atoms, and aralkyl of the formula 3 l c l wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms and haloalkyl having a maximum of4 carbon atoms and a maximum of 3 halogen atoms; R is selected from the group consisting of hydrogen and alkyl having a maximum of 4 carbon atoms; R is independently selected from the group consisting of alkyl having a maximum of 4 carbon atoms, alkoxy having a maximum of 2 carbon atoms and halogen; p is one of the integers zero to one; and q is one of the integers zero to two; R' is selected from the group consisting of -CH CH Ophenyl, CH CH O--naphthyl, -CH CH=CH--phenyl, the group wherein R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms, chloroalkyl having a maximum of 3 carbon atoms and a maximum of 3 halogen atoms, chloroalkenyl having a maximum of 3 carbon atoms and 3 halogen atoms, provided that only one of R and R is alkenyl or chloroalkenyl; R is selected from the group consisting of halogen, alkyl having a maximum of 4 carbon atoms, nitro, alkoxy having a maximum of 3 carbon atoms, and r is one of the integers zero to two, the group Alia-gr wherein R is selected from the group consisting of phenyl and naphthyl.

Another preferred embodiment of this invention are the compounds of the formula wherein R and R are independently selected from the group consisting of hydrogen and alkyl having a maximum of 6 carbon atoms; and R and R are independently selected from the group consisting of hydrogen, alkyl having a maximum of 15 carbon atoms, alkenyl having a maximum of 10 carbon atoms, haloalkyl having a maximum of 6 carbon atoms and a maximum of 4 halogen atoms; cycloalkyl having 3 to 7 ring carbon atoms, substituted cycloalkyl having 3 to 7 ring carbon atoms and a maximum of 4 carbon atoms, phenyl, substituted phenyl having a maximum of 2 substituents said substituents being independently selected from the group consisting of halogen and alkyl having a maximum of 4 carbon atoms; CH CH Ophenyl, -CH CH Onaphthyl, -Cl-l CH=CHphenyl, the group wherein R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms, chloroalkyl having a maximum of 3 carbon atoms and a maximum of 3 halogen atoms, chloroalkenyl having a maximum of 3 carbon atoms and 3 halogen atoms, provided that only one of R and R can be alkenyl or chloroalkenyl; R is independently selected from the group consisting of halogen, alkyl having a maximum of 4 carbon atoms, nitro, alkoxy having a maximum of 3 carbon atoms, and r is one of the integers zero to two, the group 14 12 15 R r l l c cu wherein R is selected from the group consisting of alkyl and alkenyl each having a maximum of 4 carbon atoms, provided that R is other than alkenyl when either R or R is alkenyl or chloroalkenyl, and R", R, R and r are as previously defined, and the group wherein R is selected from the group consisting of phenyl and naphthyl.

Another preferred embodiment of this invention are the compounds of the formula c Z6 R21 L20 g5 wherein R is selected from the group consisting of hydrogen, alkoxy having a maximum of 6 carbon atoms, alkyl having a maximum of 6 carbon atoms and alkenyl having a maximum of 6 carbon atoms; R is selected from the group consisting of alkyl having a maximum of 12 carbon atoms, alkenyl having a maximum of 10 carbon atoms, haloalkyl having a maximum of 6 carbon atoms and maximum of 4 carbon atoms, cycloalkyl having 3 to 7 ring carbon atoms and a maximum of 4 chain carbon atoms, phenyl, substituted phenyl having a maximum of 2 substituents, said substituent being selected from the group consisting of halogen, alkyl having a maximum of 4 carbon atoms and COOl-l, and the group wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms, alkenyl having a maximum of 3 carbon atoms, and haloalkyl having a maximum of4 carbon atoms and a maximum of 3 halogen atoms; R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms and haloalkyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms; R is independently selected from the group consisting of alkyl having a maximum of4 carbon atoms, alkoxy having a maximum of 2 carbon atoms, COOH and halogen; p is one of the integers zero to two; R R, Z and Z are as previously defined.

Another preferred embodiment of this invention are the compounds of the formula wherein R is selected from the group consisting of hydrogen, alkoxy having a maximum of 6 carbon atoms, alkyl having a maximum of 6 carbon atoms and alkenyl having a maximum of 6 carbon atoms; R is selected from the group consisting of alkyl having a maximum of 12 carbon atoms, alkenyl having a maximum of 10 carbon atoms, haloalkyl having a maximum of 6 carbon atoms and a maximum of 4 carbon atoms, cycloalkyl having 3 to 7 ring carbon atoms and a maximum of 4 chain carbon atoms, phenyl, substituted phenyl having a maximum of two substituents, said substituent being selected from the group consisting of halogen, alkyl having a maximum of 4 carbon atoms and -COOH, and the group wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of4 carbon atoms, alkenyl having a maximum of 3 carbon atoms, and haloalkyl having a maximum of4 carbon atoms and a maximum of three halogen atoms; R is selected from the group consisting of hydrogen, alkyl having a maximum of 4 carbon atoms and haloalkyl having a maximum of 4 carbon atoms and a maximum of 3 halogen atoms; R is independently selected from the group consisting of alkyl having a maximum of 4 carbon atoms, alkoxy having a maximum of 2 carbon atoms, -COOH and halogen; p is one of the integers zero to two; and q is one of the integers zero to two; Z is oxygen; R is selected from the group consisting of hydrogen, alkyl having a maximum of 6 carbon atoms and alkenyl having a maximum of 6 carbon atoms; R is selected from the group consisting of alkoxy having a maximum of 6 carbon atoms, chloroalkenyl having a maximum of 6 carbon atoms and a maximum of 3 halogen atoms, the group c and the group (f CH- 7 wherein R", R R, R and r are as previously defined; and R is selected from the group consisting of hydrogen, alkyl having a maximum of 12 carbon atoms and alkenyl having a maximum of 12 carbon atoms; R and R can with the nitrogen form the group consisting of 17 Li S R S 17 N S s and N S O The novel compounds of this invention possess herbicidal activity.

The term plant asused herein and in the appended claims, is inclusive of dormant seeds, germinant seeds, germinative seeds, emerging seedlings and established woody and herbaceous vegetation including the roots and above-ground portions.

The term control. as used herein and in the appended claims is inclusive of the actions of l) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying or otherwise diminishing the occurrence and activity of plants and is applicable to any of the stated actions, or any combination thereof.

The terms alkyl, alkenyl", alkynyl, alkylene and the like as used herein and in the appended claims are inclusive of both straight and branched chain radicals.

In the above formula R -l-[Bican be such as methyl, ethyl, n-propyl, isopropy'l, n-butyl, sec-butyl, isobutyl, tert-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetra-decyl, hexadecyl, octadecyl and the various homologues and isomers of alkyl having from 1 to 12 carbon atoms, alkenyl such as vinyl, allyl, n-butenyl-l, n-butenyl2, n-pentenyl-Z, n-hexenyl-2, 2,3-dimethylbutenyl-2, n-heptenyl, n-decenyl, ndodecenyl and the various homologues and isomers of alkenyl having 2 to 12 carbon atoms, alkynyl such as propargyl, n-butynyl-2, n-pentynyl-3 and the various homologues and isomers of alkynyl having from 3 to l2 carbon atoms, alkoxy such as methoxy, ethoxy, n propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, hexoxy, heptoxy, dodecoxy, and the various homologues and isomers of alkoxy having from 1 to 12 carbon atoms, alkenoxy such as allyloxy, nbutenoxy, n-pentenoxy, n-hexenoxy, 2,3- dimethylbutenoxy, n-heptenoxy, n-dodecenoxy and the various homologues and isomers of alkenoxy having 2 to 12 carbon atoms, alkynoxy such as propargoxy, nbutynoxy and the various homologues and isomers of alkynoxy having from 3 to 12 carbon atoms, and acyl such as methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, heptylcarbonyl, decylcarbonyl, hexadecylcarbonyl, allylcarbonyl, n-butenylcarbonyl, n-pentenylcarbonyl, 2,3-dimethylbutenylcarbonyl, n-decenylcarbonyl, propargylcarbonyl, n-butynylcarbonyl and the various homologues and isomers of acyl of not more than 12 carbon atoms,

In the above formula R O -[-R O+,,,R can be alkoxyalkyl, alkenoxyalkyl, alkoxyalkoxyalkyl, alkenoxyalkoxyalkyl, dialkoxyalkyl, alkenoxy(alkoxy)alkyl, alkenoxyalkoxy(alkoxy) alkyl and alkoxyalkoxy(alkoxy)alkyl such as Z-methoxyethyl, 4-ethoxy-2- methylbutyl, Z-ethoxyethyl, 3-propoxypropyl, 4- methoxybutyl,4-methoxy-2-ethylbutyl, 4-butoxybutyl, 2-allyloxyethyl, 2-butenoxyethyl, 4-butenoxybutyl, 2- (Z-methoxyethoxy) ethyl, 2-(2-butoxyethoxy)ethyl, 4-( 3-methoxypropoxy)butyl, 2-( 3-allyloxypropoxy)ethyl, Y 2-(2-butenoxyethoxy)ethyl, 4,4- dimethoxybutyl, 2,2-diethoxyethyl, 2,4- dimethoxybutyl, 4,4-diethoxybutyl, 2-methoxy-4- allyloxybutyl, 2-ethoxy-2-propenoxyethyl, 4-(2- allyloxyethoxy)-2-methoxybutyl, 2-(4- methoxybutoxy)-2-methoxyethyl, 4-(2- methoxyethoxy)-4-butoxybutyl and the like.

15 16 In the formula R can be hydrogen, the alkyl, alkenyl bromohexyl, 2,4-dichlorohexyl, l,3-dibromohexyl, and alkynyl listed above for R -B],,, alkoxyalkyl and l,3,4-trichlorohexyl, chloroheptyl, bromoheptyl, fluoalkenoxyalkyl such as methoxyethyl, ethoxyethyl, proroheptyl, 1,3-dichloroheptyl, l,4,4-trichloroheptyl, 2,4-dichloromethylheptyl, chlorooctyl, bromooctyl, poxypropyl, methoxybutyl, butoxybutyl, allyloxyethyl, 5 iodooctyl, 2,4-dichloromethylhexyl, 2,4-dichlorooctyl, butenoxyethyl, butenoxybutyl, ethoxyoctyl, butoxyde- 2,4,4-trichloromethylpentyl, 1,3,5-tribromooctyl and cyl, butenoxyoctyl and the like; cycloalkyl, alkylcythe halogenated straight and branched chain nonyl cloalkyl,cycloalkenyl and alkylcycloalkenyl such as cydecy], undecyl, dodecyl, tridecyl, tetradecyl, pentaclopentyl, S-methoxycyclopentyl, 5-methylcyclopentyl, decyl, hexadecyl, heptadecyl and octdecyl; haloalkenyl 3,4-dimethylcyclopentyl, 2,5-dimethylcyclopentyl, such as chlorovinyl, bromovinyl, chloroallyl, bromoal- 3,4-dimethylcyclopentyl, S-(tert-butyl)-cyclopentyl, lyl, 3-chloro-n-butenyl-l, 3-chloro-n-pentenyl-l, l-cyclohexyl, 3-methylcyclohexyl, 3,4-dimethylcy- 4-chloro-n-hexenyl-2, 34-dichloromethylpentenyl-l, clohexyl, 2,4-dimethylcyclohexyl, 3-methylcyclohexyl, 3-fluoro-n-heptenyl-l, l,3,3-trichloro-n-heptenyl-5, 4-butylcyclohexyl, 2,6-dimethylcyclohexyl, 3,3-dime- I,3,5-trichloro-n-octenyl-6, 2,3,3-trichloromethylthylcyclohexyl, 6-(tert-butyl) cyclohexyl, cycloheptyl, l5 pentenyl-4 and the various homologues and isomers of 3-methylcycloheptyl, 3,4-dimethylcycloheptyl, 7- haloalkenyl having 2 to 12 carbon atoms; haloaryl such methylcycloheptyl, 4,5-dimethylcycloheptyl, 6- as o-chlorophenyl, m-chlorophenyl, m-bromophenyl, methylcycloheptyl, 7-methylcycloheptyl, 7-(tertp-chlorophenyl, 2,4-dichlorophenyl, 3,5- butyl)-cycloheptyl, 4-is0p 0py y l0heptyl, an he dichlorophenyl, 2,5-diiodophenyl, and the like. like, and aryl, alkaryl, aralkyl, and aralkenyl Such as The meta bifunctional compounds of this invention' pheny lyl, hylph nyl, ylph nyl, Xyly can be prepared by a process represented by the folbutylphenyl, diethylphenyl, diphenylmethyl, benzyl, lowing syntheses: l

1 a 1 R 3 i; 2

2 6] NH RCX or-- KT I 2 E Y (R (1)2 phenylethyl, and the like. wherein Y is SH OH or N0 X is chloro or bromo Representative R include by way of example, hyand R and R are as previously defined drogen, haloalkyl such as chloromethyl, iodomethyl, When Y is hydroxyl or mercapto the following synbromomethyl, fluoromethyl, chloroethyl, iodoethyl, thesis represents a mode of preparation of the desired bromoethyl, dichloroethyl, diiodoethyl, dibromoethyl, compounds:

2 R 0 l I 2 R 0 N c R 2 lo c R R N c 0 k LO 0H 6 c mm l R o R o 2 I 2 10 g m- C N-C-H R C y g/ 1 R O ll 0Na. "3 R chloro-n-propyl, bromo n-propyl, iodoisopropyl, wherein R ,R R, R", Z and X are as previously debromo-n-butyl, bromo-tert-butyl, 1,3,3-trichlorobutyl, fined. l,3,3-trlbomobutyl, chloropentyl, bromopentyl, 2,3- When Y is nitro the following synthesis represents a dichloropentyl, 3,3-dibromopentyl, chlorohexyl, mode of preparation of the desired compounds:

r e R O f N C R H 2 H2 r N c F.

R1 9 7 N c R2 R23 E z ,N C X 9 NH R24 l n 2 s (9) N C R XC Z R wherein R, R R R, R R R R R, Z, Z Z, Z and X are as previously defined.

The above reactions are represented equations as to modes of preparation of the desired compounds. Other modes are available and are listed in the literature and the following examples.

' ln reaction (1), where Y is hydroxy or mercapto, the reaction of the 3'-hydroxyamines or 3'- mercaptoamines with acyl halides or the appropriate anhydride can be carried out in various ways.

Normally it is desired for maximum yield that the amine be present in at least an equimolar amount to the acyl halide or the anhydride and preferably the halide or anhydride is in excess because of relative cost of the reagents. The reaction is suitably carried out at a temperature from about 0 to about 15C. However, higher or lower temperatures can be used, the temperature not being critical. For example, temperatures above about 40C. are generally employed when no acid acceptor is used and often in the range of about 80l50c.

With an acyl halide Reaction 1 is preferably carried out in the presence of an acid acceptor and an inert organic medium. When reactive acyl halides are utilized the reaction is carried out in an aqueous medium. Aqueous organic medium, such as aqueous ethyl acetatecan also be utilized. The acid acceptor is generally present in at least equimolar amounts based on the amount of hydrogen halide formed in the reaction. Suitable acid acceptors, e.g. alkaline-acting or basic materials capable of binding the acid evolved in the reaction are the tertiary amines such as trimethylamine, triethylamine, pyridine, quaternary ammonium hydroxides, N-ethylmorpholine and the like; inorganic bases such as odium hydroxide and potassium hydroxide, sodium and potassium carbonate, bicarbonate and the like. An excess of amine reactant also serves as an acid acceptor.

With the anhydride Reaction I is preferably carried out in the presence of an aqueous medium.

The separation of the resulting reaction product, ,which are usually crystalline solids, from reaction mixture l is readily accomplished. For example, the salt, such as a tertiary amine hydrochloride salt formed during the reaction because of the presence of a tertiary amine compound therein as an acid acceptor. is separated from the product containing reaction mixture by simple means such as filtration and the solvent is removed from the resulting filtrate by stripping or distillation, preferably low temperature vacuum distillation.

R1 o y H 2 N c R a C 1:22 "7 \RZ R z 1 ll 7 N c R 7W1 r 8 21 N c Z P. 20 "5 R z The product can be pruified by any of the conventional means well known in the art, e.g. fractional distillation under reduced pressure, selective extraction, ractional distillation using a carrier gas or any suitable combination of these. Normally the product is sufficiently pure so that no recrystallization is necessary. If desired the product can be subjected to film distillation, recrystallization or a combination of both for further purification.

Reaction (2), as represented by the reaction of 3'- hydroxyanilides and isocyanates, can be carried out in a variety of ways. Reaction (2) is usually carried out with substantially equimolar amounts of reactants but a small excess of either reactant can be employed if desired. Reaction (2) can be carried out by simply admixing the reactants and heating at a suitable temperature, for example, from about 39 to about C. However, reaction temperature is not critical and higher (e.g. l00C.) or lower (e.g. 20C.) temperatures can be employed.

Reaction (2) is advantageously carried out in the presence of at least one of the acid acceptors useful in Reaction l and an inert organic media. The amount of acid acceptor (catalyst) utilized is dependent upon the nature of the isocyanate primary isocyanates requiring less catalyst than tertiary isocyanates. lnert organic media which can be used in Reaction (2) include, for example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, n-heptane, nhexane and the like, organic halides such as carbon tetrachloride, n-butylchloride, ethylenedichloride, tetrachloroethylene, chlorobenzene and the like, ethyl acetate, dimethylformamide and ethers such as diethyl ether, dibutyl ether, bis(2-methoxyethyl)ether, tetrahydrofuran and the like.

The separation of the resulting reaction product from reaction mixture (2) is readily accomplished. The solvent can be removed by filtration, stripping or distillation, preferably low temperature vacuum distillation. The product if desired can be purified by any of the conventional means well known in the art, e.g. fractional distillation under reduced pressure, selective extraction, fractional distillation using a carrier gas, film distillation, recrystallization, elution or any suitable combination of these methods.

Reaction (3) of the sodium phenates of 3- hydroxyanilides and carbamoyloxy halides is usually carried out by simply admixing the reactants and heating in the presence of an inert organic medium such as those listed above for Reaction (2). Separation of the resulting reaction product from Reaction mixture (3) is carried out by the methods described above for Reaction (2). A preferred method is to dissolve the substituted phenol in methanol and add a stoichemetric amount of 25 percent sodium methoxide in methanol. Approximately an equal volume of diethyleneglycol dimethyl ether (bis(2-methoxyethyl)ether) is added, the methanol removed under vacuum, leaving a slurry of the phenoxide in diglyme. This is heated with the carbamoyl chloride, sodium chloride precipitating. The

Hydrogenation of the nitro group may be by any of i the procedures known to those skilled in the art, such as catalytic hydrogenation; metal-acid combination such as iron-acid; metal-alcohol combination such as zinc dust or aluminum amalgams and aqueous alcohol; lithium aluminum hydride and the like.

The procedure used may depend upon the groups alsalt is filtered off, washed with diglyme" and the fil- 10 ready present on the ring. These procedures are also trate vacuum evaporated to remove the solvent. well known to those skilled in the art. The preferred The 3'-(carbamoyloxy)anilides of this invention are procedure is catalytic hydrogenation utilizing 5 percent liquid or crystalline solid materials which are generally palladium on charcoal. insoluble in water but somewhat soluble in many or- The order of addition, as will be illustrated by the folganic solvents, for example alcohols, ketones, hydrol5 lowing schemes, to the ring is not critical. carbons such as benzene, toluene, xylene and the like In the preparation of the product of reaction scheme and chlorohydrocarbons such as chlorobenzene, car- 8, the following scheme illustrates other reaction that bon tetrachloride and the like. yield the desired product and also the lack of necessity The starting m-nitrioanilines utilized in reaction for a strict order of addition.

R Q R 0 A l u H m NH R C-X N-C-R H f N. @51

\ l 7 5 ii i \/u 2 r i R ::=c=s NO? 2 N11 4 R 0 CSCl i i A s-eR l 23 /'V I B -N;-CCl 1 23 1 1 Ni-i3-ifl-ffi S i T i R lise 1 :1 I? u H], 9 R10 2 I /\r N-cu m N-CR NCS a 23 NH-CNH R NH it 24 1 O R O R O wry-CR NHC- we I H S -NH a.

2 N C 0 2a N-CNR -t COCIQ I R NH? j i N02 N03 uoa 4 H2 0 \i/ 0 {Av H u H u 2 av-cums 9 j-N-C-NHR l I l 2 NHg-R NH;

From the above reaction scheme it is seen that the 10 From the above reaction scheme it is seen that ureistarting m-nitroaniline may be reacted to form the amido group, by the known procedures which have been described previously, followed by hydrogenation of the nitro group. Conversion of the resultant amino group to a urea is illustrated by three procedures: (a) I through the formation of an isocyanate or thioisocyanate followed by reaction with an amine; (b) by reaction with a substituted carbamyl chloride; and (c) by reaction with an isothiocyanate. It will be shown later that procedure (a) substituting an alcohol for the amine reactant yields the product of reaction scheme 9.

do-amido compounds can also be prepared by first con verting mnitroaniline to the isocyanate or the isothiocyanate. These compounds are commercially available. The resultant'isocyanate is reacted with an amine to 5 yield the m-nitrourea compound. The nitro group is then reduced and the amido group formed.

In the formation of the compounds of reaction scheme 5, there can either be a stepwise formation of the amido groups starting from nitroaniline or if R and R are the same both amido groups can be formed at the same time by reaction of a m-diamine.

3,865,867 25 26 In the stepwise addition m-nitroaniline is reactedto The above reaction schemes show the interrelaintroduce the first amido group. The nitro group is then tionship of the four groups of compounds. Thereacreduced to the amino group, which can then be reacted tions, starting compounds, intermediates and/or reacto form a secondary amine followed by reaction to tants to form each group are common-to the 'groups. form an amido group or reacted directly to the amido 5 group. It will be shown hereinafter that this interrelationship If both R2 and Rm are the Same, the pp p m of the four groups also extends to their herbicidal activphenylenediamine can be reacted to form the di-amido i compound.

In the formation of the product of reactionscheme 10 The following examples will illustrate the invention. 9, the following illustrates the variety of procedures In the following examples as well as in the specification available and the different order of addition, or formaand appended claims, parts and percent are by weight tion of groups. unless otherwise indicated.

The starting m-nitroaniline can be reacted to form 65 EXAMPLE 1 either the amido group; an isocyanate or a carbanilate.

The nitro group is then reduced to the amino group and This example describes the preparation of 3'-hydroxfurther reacted to form the required amido or carbaniypropionanilide. A reaction vessel in an ice bath is late group. charged with 54.5 parts of m-aminophenol. 50 parts of about a 20 minute period, the temperature increasing to a maximum of about 10C. The reaction mixture is stirred for about 2 hours at a temperature of about 5C. The bath is removed and stirring is continued for an additional 16 hours at room temperature. The solids are removed from the reaction mixture bu filtration, washed separately with water and benzene and air dried to give 73 parts of 3'-hydroxypropionanilide, m.p. l8ll82C.

EXAMPLE 2 This example describes the preparation of 3- hydroxy-2-methylvaleranilide. A reaction vessel in an ice bath is. charged with 163.5 parts of m-aminophenyl, 165 parts of k CO 300 parts of water, 400 parts of ice and 450 parts of ethyl acetate. Valeryl chloride, 216 parts, is added dropwise with stirring over about a 90 minute period, the .temperature increasing to a maximum of about 10C. The bath is removed and stirring is continued for an additional 2 hours at room temperature. The reaction mixture is cooled to about 8C and I the solids are removed by filtration, washed separately with water and benzene and air dried to give 144 parts of 3'-hydroxy-2-methylvaleranilide, m.p. l36137C.

Calcd for C H NO C, 69.54; H, 8.27 Found: C,

7 EXAMPLE 3 This example describes the preparation of 3'- hydroxy-Z-methylpropionanilide. A reaction vessel in an ice bath is charged ith 163.5 parts of maminophenol, 165 parts of K CO 300 parts of water, 400 parts of ice and 450 parts of ethyl acetate. lsobutyryl chloride, 148 parts, is added dropwise with stirring over about a 90 minute period, the temperature rising to a maximum of about 10C. The bath is removed and stirring is continued for an additional 2 hours at room temperature. The reaction mixture is cooled to about 8C and the solids are removed by filtration, washed separately with water and benzene and air dried to give 225 parts of 3'-hydroxy-2-methylpropionanilide, m.p. l8ll82C.

Calcd for c,,,H,,No,; C, 67.01; H. 7.31 Found: C, 66.97; H, 7.32

EXAMPLE 4 This example describes the preparation of 3'- hydroxy-cinnamanilide. A reaction vessel in an ice bath is charged with 54.5 parts of m-aminophenol, 46 parts of K CO 100 parts of water and 100 parts of ethyl acetate. Cinnamoyl chloride, 92 parts, is added to the reaction mixture with stirring over about a 1 hour period, the temperature increasing to a maximum of C. The reaction mixture is stirred for about 2 hours at a temperature of about 5C. Benzene, 100 parts, is added to the reaction mixture which is then filtered. The solids are washed separately with water and benzene and air dried to give 1 17 parts of 3'-hydroxycinnamanilide, m.p. ZZZ-223C.

Calcd for C ,,H NO C, 75.30; H, 5.48; N, 5.85 Found: C, 75.53; H, 5.68; N, 5.81

EXAMPLE 5 This example describes the preparation of 3- hydroxy-Zphenylacetanilide. A reaction vessel in an ice bath is charged with 54.5 parts of m-aminophenol, 46 parts of K CO 100 parts of water and 100 parts of ethyl acetate. Phenylacetyl chloride, 85 parts, is added LII to the reaction mixture with stirring over about a 1 hour period, the temperature increasing to a maximum of 15C. The reaction mixture is stirred for about 2 hours at a temperature of about 5C. Benzene, 100 parts, is added to the reaction mixture which is then filtered. The solids are recrystallized from benzene/ethyl acetate, air dried and recrystallized from an aqueous solution of methyl alcohol to give 88 parts of product, m.p. 15ll52C.

Calcd for C H NO C, 73.99; H, 5.77; N, 6.46 Found: C, 73.82; H, 5.67; N, 6.40

EXAMPLE 6 This example describes the preparation of 3- hydroxy-2-methylacrylanilide. A reaction vessel in an ice bath is charged with 209 parts of m-aminophenol, 178 parts of K2CO 40Q p ar ts of water, 4 00 parts of ice and 500 parts of ethyl acetate. Methylacrylyl chloride, 200 parts, is added over about a 90 minute period, the temperature increasing to a maximum of about 10C. The reaction mixture is stirred for about 30 minutes at a temperature of 5to 10C. The bath is removed and 300 ml. of benzene are added to the reaction mixture. The reaction mixture is filtered and the solids are washed separately with (l) a 50:50 ethyl acetate/benzene mixture, (2) water, (3) a 5 percent aqueous solution of HCl and (4) water. The solids are dried under vacuum to give 309 parts of 3'-hydroxy-2- methylacrylanilide, m.p. I l 73-175C.

Calcd for C H NO C, 67.78; H, 6,26; N, 7.90 Found: C, 67.69; H, 6.21; N, 7.87

EXAMPLE 7 This example describes the preparation of 3'- hydroxy-2,2,2-trichloroacetanilide. A reaction vessel equipped with external cooling is charged with 88 parts of m-aminophenol, parts of K CO ,200 parts of water and 500 parts of ice. Trichloroacetyl chloride, 173 parts, is added with stirring over about a 2 hour period, the temperature increasing to a maximum of about 10C. The reaction mixture is stirred for about 16 hours at a temperature of about 5C. The bath is removed and the oil layer of the reaction mixture is separated by decantation, admixed with water and ethyl ether and evaporated under vacuum to remove the sol- .vent. The residue crystals are dissolved in hot methyl alcohol, and the solution filtered. The filtrate is combined with water, cooled to about l5C. and filtered to recover the solid product which is then washed with a 50 percent aqueous solution of methyl alcohol (cold) and air dried. The product amounts to about parts, m.p. l22-l23C.

Calcd for C H C1 NO C, 37.75; H, 2.38; Cl, 41.79 Found: C, 37.70; H, 2.39; Cl, 41.62

EXAMPLE 8 This example describes the preparation of 3- (methylcarbamoyloxy)propionanilide. A reaction vessel containing 100 parts of anhydrous dimethylformamide (DMF) and 20 parts of 3-hydroxypropionanilide is charged with 10 parts of methyl isocyanate. No apparent reaction occurs until one part of triethylamine is added at which time the temperature increases exothermically to about 38C. The reaction mixture is heated to about 80C, cooled slightly and vacuum distilled to remove'DMF. The residue is dissolved in methyl alcohol and filtered. The filtrate is heated, admixed with water and cooled. The solids which form 29 upon cooling are removed by filtration togive 17.5 parts of product, m.p. l56160C.

Calcd for C H N Q C, 59.45; H, 6.35; N, 12.6 Found: C, 59.51; H, 6.43 N, 12.47 7

EXAMPLE 9 This example describes the preparation of 3-(tbutylcarbamoyloxy)propionanilide. A reaction vessel containing 100 parts of anhydrous dimethylformamide (DMF) and 20 parts of 3'-hydroxypropionanilide is charged with 12 parts of t-butyl isocyanate. N apparent reaction occurs until one part of triethylamine is added at which time the temperature increases exothermically to about 38C. The reaction mixture is heated to about 80C, cooled slightly and vacuum distilled to remove DMF. The solid residue is crystallized from hot methyl alcohol to give 13 parts of product, m.p. 197C at 0.2C/minute.

Calcd for C H N Q z C, 63.62; H, 7.63; N, 10.60 Found: C, 63.55; H, 7.64; N, 10.71

EXAMPLE 10 This example describes the preparation of 2-methyl- 3-(methylcarbamoyloxy)propionanilide. A reaction vessel containing 100 parts of anhydrous dimethylformamide (DMF) is charged with 27 parts of 3- hydroxy-2-methylpropionanilide and 1 1.4 parts of methyl isocyanate. No apparent reaction occurs until one part of triethylamine is added to the reaction mixture at which time the temperature increase exothermically to about 45C. The reaction mixture is heated to about 90C, cooled slightly and the DMF removed by evaporation under vacuum. The solid residue is dissolved in hot methyl alcohol and crystallized from an aqueous methyl alcohol solution to give 19 parts of product, m.p. 157.5-l58.5C.

Calcd for C H N O z C, 61.00; H, 6.83; N, 11.86 Found: C, 60.92; H, 6.79; N, 11.70

EXAMPLE 11 This example describes the preparation of 2-methyl- 3-(methylcarbamoyloxy)propionanilide. A reaction vessel containing 100 parts of ethyl acetate and 27 parts of 3'-hydroxy-2-methylpropionanilide is charged with 1 1.4 parts of methyl isocyanate and one part of triethylamine. The reaction mixture is refluxed for about 1 hour, cooled and filtered. The solid is washed with ethyl acetate and air dried to give 36 parts of product, m.p. 157.5-158.5C.

Calcd for C, H, N O C, 61.00; H, 6.83; N, 11.86 Found: C, 60.89; H, 6.92; N, 11.72

EXAMPLE 12 This example describes the preparation of 3- (ethylcarbamoyloxy)-2-methylacrylanilide. A reaction vessel is charged with 100 parts of ethyl acetate, 17.7 parts of 3'-hydroxy-2-methylacrylanilide, 10.7 parts of ethyl isocyanate and one part of triethylamine. The reaction mixture is heated at reflux with stirring for about one hour and then 100 parts of benzene are added. After cooling, the solids are removed from the reaction mixture by filtration, washed with an ethyl acetate/benzene mixture and air dried to give 17.5 grams of product, m.p. 143-145C.

Calcd for C H N O C, 62.89; H 6.50; N, 11.28 Found: C, 62.91; H, 6.70; N, 11.24

30 EXAMPLE 13 The procedure of Example 12 is substantially repeated using 15 parts of n-butyl isocyanate in place of the 10.7 parts of ethyl isocyanate. The 3'-(tbutylcarbamoyloxy)-2-methylacrylanilide amounts to 20.5 parts, m.p. 147-148C.

Calcd for C, H .,N O C, 65.20; H, 7.30; N, 10.14 Found: C, 65.21; H, 7.47; N, 10.24

EXAMPLE 14 The procedure of Example 12 is substantially repeated using 13.8 parts of cyclohexyl isocyanate in place of 10.7 parts of ethyl isocyanate. The 3- (cyclohexylcarbamoyloxy)-2-methylacrylanilide amounts to 15.5 parts, m.p. 19l-193C.

Calcd for C H N O C, 67.53; H, 7.33: N, 9.27 Found: C, 67.40; H, 7.40; N, 9.10

EXAMPLE 15 The procedure of Example 12 is substantially re peated using 16.9 parts of p-chlorophenyl isocyanate in place of the 10.7 parts of ethyl isocyanate. The 3'-(pchlorocarbamoyloxy)-2-methylacrylanilide amounts to 27.7 parts, m.p. l76l77C.

Calcd for C H ClN O C, 61.73; H, 4.57; N, 8.47 Found: C, 61.86; H, 4.75; N, 8.52

EXAMPLE 16 A reaction vessel is charged with parts of ethyl acetate, 17.7 parts of 3'-hydroxy-Z-methylacrylanilide, 23.3 parts of l,l,3,3-tetramethylbutyl isocyanate and 4 parts of triethylamine. The reaction mixture is heated at reflux for about 18 hours with stirring, and then 100 parts of benzene and 50 parts of hexane are added. The reaction mixture is cooled to l5C and filtered. The solids are washed with hexane and recrystallized from aqueous methyl alcohol to give 12.5 parts of 3'- 1,1 ,3,3-tetramethylbutylcarbamoyloxy)-2- methylacrylanilide, m.p. 1 16-120C.

Calcd for C H N O z C, 68.64; H, 8.49; N, 8.43 Found: C, 68.56; H, 8.42; N, 8.38

EXAMPLE 17 A reaction vessel is charged with 100 parts of ethyl acetate, 16.3 parts of 3'-hydroxyacrylanilide, 29.5 parts of octadecyl isocyanate and one part of triethylamine. The reaction mixture is heated at reflux for about 1 hour, cooled to 20C and filtered. The solids are washed with ethyl acetate and air dried to give 40.5 parts of 3'-(octadecylcarbamoyloxy)acrylanilide, m.p. l24-l26C.

Calcd For C H N O C, 73.32; H, 10.11; N, 6.11 Found: C, 73.50; H, 10.24; N, 6.26

EXAMPLE 18 The procedure of Example 17 is substantially repeated using 17.7 parts of 3'-hyd:roxycrotonanilide in place of the 16.3 parts of 3-hydroxyacrylanilide. The 3-(octadecylcarbamoyloxy) crotonanilide amounts to 41.5 parts, m.p. 134-136C.

Calcd for C I-1 N 0 C, 73.68; H, 10.42; N, 5.93 Found: C, 73.59; H, 10.20; N, 6.09

EXAMPLE 19 The procedure of Example 17 is substantially repeated except that 17.7 parts of 3-hydroxycyc1opropanecarboxanilide is used in place of the 16.3 parts of 3'hydroxyacrylanilide. The -3- (octadecylcarbamoyloxy)cyclopropanecarboxanilide amounts to 39.5 parts, m.p. l47.5149.5C.

Calcd for C ,;H N O C, 73.32; H, 10.11; N, 6.11 Found: C, 73.51; H, 10.32; N, 5.78

EXAMPLE 20 A reaction vessel is charged with 100 parts of ethyl acetate and 17.7 parts of 3'-hydroxy-2- methylacrylanilide and heated with stirring to about 65C. Phenyl isocyanate, 12 parts, is added. No apparent reaction occurs until one part of triethylamine is added to the reaction mixture. After a slight exothermic increase in temperature, the reaction mixture is heated at reflux for 1% hour, cooled and filtered. The solids are washed with ethyl acetate and-air dried to give 22.8 parts of 3-(phenylcarbamoyloxy)-2- methylacrylanilide, m.p. 177-l78C.

Calcd for C, H, N O C, 68.91; H, 5.44; N, 9.45 Found: C, 68.76; H, 5.54; N, 9.67

EXAMPLE 21 The procedure of Example 20 is substantially repeated using 16.9 parts of l-naphthyl isocyanate in place of the 12 parts of phenyl isocyanate. After addition of the one part of triethylamine, 100 additional parts of ethyl acetate are added. The reaction mixture is then refluxed for about /2 hour, cooled and filtered. The solids are washed with ethyl acetate and air dried to give 31.5 parts of 2-methyl-3-( l-naphthylcarbamoyloxy)acrylanilide, m.p. l95-l96C.

Calcd for C H N O C, 72.82; H, 5.24; N, 8.09 Found: C, 72.63; H, 5.27; N, 8.24

EXAMPLE 22 The procedure of Example 20 is substantially repeated using 15.4 parts of o-chlorophenyl isocyanate in place of the 12 parts of phenyl isocyanate. The 3-(ochlorophenylcarbamoyloxy)-2-methylacrylanilide amounts to 21 parts, m.p. l20-123C.

Calcd for C H, ClN O C, 61.73; H, 4.57; N, 8.47 Found: C, 61.65; H, 4.56; N, 8.37

EXAMPLE 23 The procedure of Example is substantially repeated using 14.9 parts of p-methoxyphenyl isocyanate in place of the 12 parts of phenyl isocyanate. The 3-(pmethoxyphenylcarbamoyloxy)-2-methylacrylanilide amounts to 26.5 parts, m.p. 175-176C.

Calcd for C H N O C, 66.25; H, 5.56; N, 8.58 Found: C, 66.52; H, 5.79; N, 8.36

EXAMPLE 24 EXAMPLE 25 This example describes the preparation of N- isopropyl-3-(methylcarbamoyloxy)propionanilide. A reaction vessel is charged with 20.7 parts of 3'- hydroxy-N-isopropylpropionanilide, 100 parts of ethyl acetate, 6.9 parts of methyl isocyanate and one part triethylamine. The reaction mixture is refluxed with stirring for about 1 hour, diluted with hexane, seeded for crystal formation, and let stand for about 16 hours. The reaction mixture is filtered and the solids are washed with hexane/ethyl acetate and air dried to give 20 parts of product, m.p. 9699C.

Calcd for CHI-120N203: C, 63.62; H, 7.63; N, 10.60

Found: C, 63.80; H, 7.62; N, 10.61

EXAMPLE 26 The procedure of Example 25 was repeated using 12 parts of t-butyl isocyanate in place of the 6.9 parts of methyl isocyanate. The N-isopropyl-3-(tbutylcarbamoyloxy)propionanilide amounts to 25.5 parts, m.p. ll0-l12C.

Calcd for C, H N O C, 66.64; H, 8.55; N, 9.14

Found: C, 66.79; H, 8.59; N, 9.04

EXAMPLE 27 This example describes the preparation of 3- (dimethylcarbamoyloxy)-2-methylpropionanilide. A reaction vessel is charged with 90 parts of 3'-hydroxy- 2-methylpropionanilide, 300 parts of bis( 2- methoxyethyl)ether(diglyme) and 108 parts of 25 percent solution of sodium methoxide in methyl alcohol. The reaction mixture is stirred until solution occurs and then vacuum distilled until diglyme appears in the distillate. Dimethylcarbamoyl chloride, 54 parts, is added dropwise to the distillate over about 10 minutes, the temperature increasing exothermically to about 104C. The reaction mixture is heated to about 100C for 25 minutes, cooled and filtered. The filtrate is evaporated under vacuum to about 25 parts. The 25 parts of filtrate are combined with about 125 parts of water and the 'aqueous mixture is cooled to about 5C and filtered.

The solids are washed with water and air dried to give 109 parts of product, m.p. 120122C.

Calcd for C H N O I C, 62.38; H, 7.25; N, 11.19 Found: C, 62.20; H, 7.41; N, 11.27

EXAMPLE 28 This example describes the preparation of 3- (diphenylcarbamoyloxy)-2-methylpropionanilide. A reaction vessel is charged with 45 parts of 3'-hydroxy- 2-methylpropionanilide, 150 parts of diglyme and 54 parts of 25 percent solution of sodium methoxide in methyl alcohol. The reaction mixture is stirred until solution occurs and then vacuum distilled until diglyme appears in the distillate. Diphenylcarbamoylchloride, 58 parts, is added to the distillate with stirring, the temperature increasing exothermically to about C. The reaction mixture is heated at about 120C for /2 hour, cooled to about C and filtered. The filtrate is admixed with 250 parts of methyl alcohol, cooled to about 0C and filtered. The solids are washed with methyl alcohol and air dried to give 67 parts of product, m.p. 162.5-l63.5C.

Calcd for C H N O C, 73.78; H, 5.92; N, 7.48

Found: C, 73.66; H, 6.09; N, 7.62

EXAMPLE 29 This example describes the preparation of a portion of the reaction mixture used in Examples 30, 31 and 32. A vessel is charged with 165 parts of 3'-hydroxypropionanilide, 300 parts of diglyme and 216 parts of a 25 percent solution of sodium methoxide in methyl alcohol and a clear solution results. The solution is vacuum distilled until take-off temperature is 55C at a pressure of 20 mm. of mercury. The residue, a strawcolored syrup amounting to 459.5 parts, is diluted with 250 parts of diglyme to form 709.5 parts of a mixture consisting primarily of the sodium phenate of 3'-hydroxypropionanilide and diglyme.

EXAMPLE 30 A reaction vessel containing 236.5 parts of the mixture prepared in Example 29 is charged with 50 parts of l-piperidinecarbonyl chloride, the temperature increasing exothermically to about 90C. The reaction mixture is heated at about 100C for 1 hour, cooled to 50C and filtered. The filtrate is vacuum distilled to a pot temperature of about 95C. The residue is crystallized from hot methyl alcohol and the solids are washed with methyl alcohol and air dried to give 71 parts of 3'- (l-piperidinecarboxy)propionanilide, m.p. 93-94C.

Calcd for C, H N O C, 65.20; H, 7.30; N, 10.14

Found: C, 65.34; H, 7.53; N, 10.02

EXAMPLE 31 The procedure of Example 30 is substantially repeated using 94 parts of 4-morpholinecarbonyl chloride in place of the 50 parts of l-piperidinecarbonyl chloride. The 3-(4-morpholinecarboxy)propionanilide amounts to 68.5 parts, m.p. 162-l63C.

Calcd for C,.,H,,,N O.,: C, 60.42; H, 6.52; N, 10.07

Found: C, 60.20; H, 6.66; N, 10.12

EXAMPLE 32 A reaction vessel containing 236.5 parts of the mixture prepared in Example 29 is charged with 65.9 parts of methyl-(2,6-xylyl)carbamoyl chloride. The reaction mixture is heated with stirring at a temperature of about 100 to 120C for about 2- hours, cooled and filtered. The filtrate is vacuum distilled to a pot temperature of 95C. The residue is crystallized from methyl alcohol and the solids are air dried to give 91 parts of 3 N-methyl-2,6-dimethylcarbaniloyloxy )propionanilide.

Calcd for C H N O C, 69.92; H, 6.79; N, 8.58

Found: C, 69.93; H, 6.68; N, 8.60

EXAMPLE 33 This example describes the preparation of 3- (diethylthiocarbamoyloxy)propionanilide. A reaction vessel containing 33 parts of the sodium with phenate of 3-hydroxypropionanilide is charged with 32 parts of diethylthiocarbamoyl chloride, the temperature increasing to a maximum of about 85C. The reaction mixture is heated at 100C for minutes, cooled to 60C and filtered. The filtrate is allowed to stand for 16 hours and a resinous material separates. The resinous material is crystallized from methyl alcohol and air dried to give 22 parts of product, m.p. l4014lC.

Calcd for C H N O S: C, 59.97; H, 7.90; S, 11.44

Found: C, 59.85; H, 7.43; S, 11.47

EXAMPLE 34 This example describes the preparation of 3-amino- 2,2-dimethylpropionanilide. A reaction vessel, in a water bath, was charged with 525 parts m-nitroaniline,

1760 parts benzene and 340 parts pyridine. To this mixture was added, with stirring, 500 parts pivaloyl chloride over a period of about an hour, keeping the temperature between about 25 to 35C. The resultant oil was washed with warm water and the organic layer concentrated to half its volume and methylcyclohexane added. Upon cooling pale-tan crystals separated out and were removed by filtration, and washed with hexane in. p. 115-116C. A rocking autoclave was charged with 805 parts and 908 parts isopropyl alcohol and pressurized to 1000 psi with hydrogen. Reaction temperature increased as the pressure decreased reaching a temperature of 90C at 0 psi with hydrogen. Repressurized 3 times to 500 psi. When the temperature dropped to 60C and the pressure remained essentially constant, the vessel was emptied and washed with addi tional isopropanol alcohol. The combined organic was heated to reflux and filtered. Upon chilling of filtrate a solid separated which was removed by filtration, washed with percent aqueous isopropyl alcohol, and dried m.p. 155-156C.

EXAMPLE 35 This example describes the preparation of m-(2,2- dimethylpropionamido)phenylisothiocyanate. A reaction vessel was charged with 500 parts water, 500 parts ice, 373 parts and 137 parts thiophosgene. To the mixture was added, with vigorous stirring, 193 parts 3- amino-2,2-dimethylpropionanilide over about a 10 minute period. The resultant mixture was stirred for an additional 15 minutes keeping the temperature at about 6-7C. To the resultant mixture was added 396 parts hexane and the mixture stirred for about 10 minutes at about 35C. The mixture was chilled to 5C, filtered and the solid washed with hexane, then water and dried m.p. 141-142c.

EXAMPLE 36 This example describes the preparation of 1,1- dimethyl-3-[m-(2,2-dimethylpropionamido)phenyl]- thiourea. To a reaction vessel charged with 25 parts dimethylamine and 79 parts methanol was added 40 parts m-(2,2-dimethylpropionamido)phenylisothiocyanate and the resultant mixture refluxed for about 2. minutes. To the mixture was added 132 parts benzene and 87 parts toluene and the resultant mixture filtered. The filtrate was distilled under reduced pressure until crystals appeared in the residue. The distillation was continued at atmospheric pressure until the take-off temperature was about 68C. The residue, on standing crystallized. The crystals were filtered off and washed with benzene and air dried. The crystals were heated on a water bath at 50-60C and 0.1 mm. pressure for a period of 4 hours. m.p. 141.5-l42C. Recrystallized from ethyl propionate m.p. 141-142C.

EXAMPLE 37 This example describes the preparation of 3'- aminopropionanilide. m-Nitropropionanilide, prepared from m-nitroaniline and propionylchloride according to Example 34, was charged to a rocking autoclave with 897 parts isopropyl alcohol and 15 parts 5 percent Pd. on charcoal. The apparatus was purged and pressurized to 1000 psi with hydrogen. Upon rocking, the reaction temperature rose to about 125C. Cooled reaction mixture to 50C and repressurized to 500 psi with hydrogen. Reaction temperature rose to 100C. Cooled reaction mixture to 70C and repressurized to 500 psi. Reaction temperature rose to 90C. Cooled reaction mixture to 70C and repressurized to 500 psi with hydrogen. No temperature increase occurred. Maintained this temperature for about 2 hours without much loss in pressure. The mixture was filtered and the filtrate vacuumed distilled to a pot temperature of 5 about 90-100C at 0.2 mm. The residue was cooled and seeded yielding an off-white solid mp. 9293.5C. C.

EXAMPLE 38 This example describes the preparation of 1,1- dimethyl-3-(m-propionamidophenyl)urea. To a suitable reaction vessel was charged 16.4 parts 3- aminopropionanilide, 10.8 parts dimethylcarbamoyl chloride, 8.7 parts pyridine and 62 parts dioxane. The resultant mixture was stirred about /2 hour and then let stand for about 18 hours. After standing about 1 hour a brownish tar separated from solution. After standing for'about 18 hours, water was added to the mixture until the tar dissolved and the resultant mixture cooled to below 0C for about 1 hour during which time crystallization occurred. The mixture was filtered and the crystals washed with 50 percent aqueous methanol and air dried m.p. 62-70C. Recrystallized from 35 percent aqueous methanol m.p. 70.5-71.5C.

EXAMPLE 39 This example describes the preparation of 1-allyl-3- (m-propionanilide)urea. To a suitable reaction vessel was charged 8.2 parts 3'-aminopropionanilide, 52 parts dioxane and 4.6 parts allylisocyanate. The resultant mixture was heated to about 80C and 45 parts benzene added. The mixture was let stand overnight and the solid which formed on standing was removed by filtration, washed with benzene and dried m.p. l73l74C.

EXAMPLE 40 This example describes the preparation of 3'-isothiocyanatopropionanilide. To a suitable vessel was charged 75 parts thiophosgene, 500 parts ice, 300 parts water and 300 parts chloroform. To the resultant mixture was added over a minute period, with stirring, 82 parts 3 -aminopropionanilide. A solid material separated from the mixture. Due to the presence of the ice, the reaction temperature remained at about 5C for the first hour, then rose to room temperature during the second hour as the ice melted. n-Hexane, 198 parts was added'to the mixture, stirred a few minutes and filtered. The product a whitish-tan powder was washed with water then hexane and dried m.p. 102-102.5C.

EXAMPLE 41 file. This solution was cooled to below 0C and maintained at this temperature overnight. The crystals which separated out on standing, were removed by filtration, washed with water and air dried m.p. 129-130C.

EXAMPLE 42 methanol and air dried m.p. 126127C.

The above product was charged to a rocking autoclave with 487 parts dioxane and 5 parts 5 percent pa1 ladium on charcoal. Autoclave was pressurized with hydrogen to 1000 psi and the autoclave rocked and repressurized as needed until uptake of hydrogen had substantially stopped. The mixture was filtered and the filtrate vacuum distilled until about A; of its volume had been removed. To the residue was added 66 parts methanol and the mixture heated to reflux, cooled, filtered and the filtrate heated to reflux. To this solution was added 300 parts water, the mixture cooled to below 0C and maintained at this temperature overnight. The mixture was then distilled until about of its volume was removed. A thick mass separated from solution which was removed and dissolved in 198 parts hot isopropanol, filtered and 220 parts benzene added to the filtrate. The resultant mixture was in an ice bath and seeded. The resultant precipitate was removed by filtration, washed with benzenethylacetate solution and air dried m.p. l25l26C.

EXAMPLE 43 This example describes the preparation of 1,1- dimethyl-3-[3'-(2,2,2- trimethylacetamido)pheny1]urea. To a suitable reaction vessel was added 36 parts 1,1-dimethyl-3-(maminophenyl)urea, 28 parts potassium carbonate, parts ethyl acetate 200 parts ice and 50 parts water. To the resultant mixture was added, with stirring, 36 parts pivaloyl chloride over a 20 minute ,period. The mixture was then stirred about 1 hour and an additional 90 parts ethyl acetate added. The water layer was separated. The organic layer was heated to about 65C and then cooled. The desired product which separated as a solid was removed by filtration, washed with a benzene-hexane mixture, then water and dried. The product was recrystallized from methanol m.p. 192-193C.

EXAMPLE 44 This example describes the preparation of 3'- propionamidocyclopropylcarboxanilide. To a suitable reaction vessel was charged 16.2 parts 3- aminopropionanilide, 13.8 parts potassium carbonate, parts water, 200 parts ice and 90 parts ethyl acetate. To this mixture was added, with stirring, a solution of cyclopropylcarbonyl chloride in benzene (prepared from 15.8 parts cyclopropylcarbonyl chloride and 26 parts benzene) over a 5 minute period. To the resultant mixture was added 99 parts n-hexane and then stirring continued for an additional /2 hour. The mixture was filtered and the solid, which is the desired product, was washed with benzene, water air dried. Solid recrystallized from aqueous methanol m.p. l99-200C.

EXAMPLE 45 The preparation of 3'-crotonamidopropionanilide was carried out by the procedure described in Example 44, substituting 15.8 parts crotonyl chloride for the cyclopropylcarbonyl chloride. The product, after recrystallization from aqueous methanol, melted at l95-l97C.

EXAMPLE 46 This example describes the preparation of 3'-(2,2- dimethylvaleramido)2,2-dimethylvaleranilide. To a suitable reaction vessel, cooled in a water bath, was charged 87 parts m-phenylenediamine, 790 parts acetone and 190 parts triethylamine. To this solution was added, with stirring, 260 parts 2,2-dimethylvaleryl chloride. The resultant solution was added to 1000 parts water, whereupon an oil separated out which crystallized. The solid, which is the desired product, was washed with 5 percent hydrochloric acid, 5 percent sodium hydroxide, water and dried m.p. l09-1 11C.

EXAMPLE 47 The preparation of 3'-(2,2-dimethylpropionamido)- 3,3'dimethylbutyranilide was carried out by the procedure described in Example 44, substituting 20.2 parts 3,3-dimethylbutyryl chloride for the cyclopropylcarbonyl chloride. The desired product melted at l84-l85C.

Analysis Calcd: C, 70.31; H, 9.03; N, 9.65

Found: C, 70.39; H, 9.14; N, 9.50

EXAMPLE 48 The preparation of 3'-(2-methylvaleramido)-2,2,3- trimethyl-4-pentenanilide was carried out by the procedure described in Example 44, substituting 20.6 parts 3 -amino-2-methylvaleranilide for the 3 aminopropionanilide and 24.1 parts of 4-pentenoyl chloride for the cyclopropylcarbonyl chloride. The desired product melted at l12-115C.

Analysis, Calcd: C, 72.91; H, 8.87; N, 8.51

Found: C, 73.04; H, 9.24; N, 8.32

EXAMPLE 49 This example describes the preparation of 3'- (propionamido)-2,2,-dimethyl-4-pentenoanilide. To a suitable reaction vessel was charged 8.2 parts 3- aminopropionanilide, 7 parts potassium carbonate, parts water, 31 parts benzene, 13 parts toluene and 50 parts ice. To this mixture was added, with stirring, in one portion a benzene solution of 2,2-dimethyl-4- pentenoyl chloride (prepared from 8.8 parts 2,2dimethyl-4-pentenoyl chloride and 22 parts benzene). The resultant mixture was stirred for 5 minutes and then warmed, with stirring for about minutes until a temperature of about 25C was obtained. To this mixture was added 66 parts n-hexane and the mixture, after stirring, filtered and the desired product, which was a solid, washed with hexane, water and air dried m.p. ll9.5l21.5C. Recyrstallized from benzene m.p. 123l25C.

Analysis, Calcd: C, 70,24; H, 7.75; N, 10.24

Found: C, 70.12; H, 7.69; N, 10.10

EXAMPLE This example describes the preparation of methyl maminocarbanilate. To a suitable reaction vessel, cooled in an ice bath, was charged 500 parts m-nitroaniline,

315 parts potassium carbonate, 800 parts water, 800 parts ice and 900 parts ethylacetate. To this mixture, at below about 15C, was added over about a 2 hour period with stirring 380 parts methyl chloroformate. To the resultant mixture was added 330 parts n-hexane and the mixture stirred for an additional 2 hours at a temperature in the approximate range of 25-30C. The mixture was filtered and the product washed with a 50:50 n-hexane-ethyl acetate solution, water and air dried m.p. l48150C.

The above solid was charged to a rocking autoclave and 9 parts 5 percent palladium on charcoal and 1236 parts dioxane. The autoclave was purged and charged with hydrogen to 800 psi. On rocking the reaction temperature increased to about 80C as the pressure decreased. The autoclave was repressurized to 500 psi when necessary until the pressure remained essentially constant at about C. The mixture was filtered and the filtrate vacuum distilled to a pot temperature of 80C at 0.2 mm. pressure. The residue, an oil, crystallized on standing overnight. Recrystallized from aqueous methanol and then an ethyl acetate-toluene methyl-cyclohexane solution m.p. 71-71.5C.

EXAMPLE 51 This example describes the preparation of methyl m- (2-methylvaleramido)carbanilate. To a suitable reaction wheel was charged with 16.6 parts methyl maminocarbanilate, 18 parts potassium carbonate, 100 parts water, 300 parts ice and 89 parts ethyl propionate. To this mixture was added over a 10 minute period, with stirring, a benzene solution of 2-methylvaleroyl chloride (20.2 parts Z-methylvaleroyl chloride and 52.8 parts benzne). The mixture was heated to about C, then let stand overnight. Crystals separated on standing. The crystals were removed by filtration, washed with water and ethyl acetate-hexane solution and air dried m.p. ll0-1l2C.

EXAMPLE 52 This example describes the preparation of methyl mpropionamidothionocarbanilate. To a suitable reaction vessel was charged with m-propionamidophenyl isothiocyanate (prepared from m-aminopropionanilide and thiophosgene), parts methanol and 7.3 parts tri ethylamine and the mixture refluxed for about 14 hours. The mixture was cooled and the mixture was vacuum evaporated leaving a solid residue. The solid was dissolved in 73 parts methanol, the mixture filtered and the filtrate heated to about 60C, about 50 parts water added, seeded and cooled. The desired product was separated and dried m.p. Il50152C.

EXAMPLE 53 This example describes the preparation of methyl mpropionamidothiolcarbanilate. To a suitable reaction 

1. A COMPOUND OF THE FORMULA
 2. A compound in accordance with claim 1 which is 3''-(N-alpha-t-butyl-4''''-methoxybenzylcarbamoyloxy)acetanilide.
 3. A compound in accordance with claim 1 which is 3''-(N-alpha-methyl-4''''-chlorobenzylcarbamoyloxy)acetanilide.
 4. A compound in accordance with claim 1 which is 3''-(N-alpha-methylbenzylcarbamoyloxy)propionanilide.
 5. A compound in accordance with claim 1 which is 3''-(N-methyl-N-1-methyl-2-phenylethylcarbamoyloxy)2-methylvaleranilide.
 6. A compound in accordance with claim 1 which is 3''-(N-1,1-dimethyl-2-phenylethylcarbamoyloxy)propionanilide.
 7. A compound in accordance with claim 1 which is 3''-(N-methyl-N-4''''-chlorobenzylcarbamoyloxy)propionanilide.
 8. A compound in accordance with claim 1 which is 3''-(N-methyl-N-benzylcarbamoyloxy)2,2-dimethylvaleranilide.
 9. A compound in accordance with claim 1 which is 3''-(N-methyl-N-alpha-methylbenzylcarbamoyloxy)propionanilide.
 10. A compound in accordance with claim 1 which is 3''-(N-methyl-N-2'''',4''''-dichlorobenzylcarbamoyloxy)propionanilide.
 11. A compound in accordance with claim 1 which is 3''-(N-alphamethylbenzylcarbamoyloxy)-2-methylacrylanilide.
 12. A compound in accordance with claim 1 which is 3''-(N-alphamethylbenzylcarbamoyloxy)-2-methylpropionanilide. 